Methods for preparing organopolysiloxanes using diaryloxytitanium oxide catalysts



United States Patent 3,431,229 METHODS FOR PREPARING ORGANOPOLY- SILOXANES USING DIARYLOXYTITANIUM OXIDE CATALYSTS Leon Levene, Toledo, Ohio, assignor to Owens-Illinois, Inc, a corporation of Ohio No Drawing. Filed July 12, 1967, Ser. No. 652,725 US. Cl. 26033.4 26 Claims Int. Cl. C08f 45/34, 45/28 ABSTRACT OF THE DISCLOSURE Methods for hydrolyzing trifunctional organic silanes such as methyltrialkoxysilane, phenyltrialkoxysilane, or mixtures thereof at neutral conditions using a diaryloxytitanium oxide hydrolysis catalyst such as diphenoxytitanium oxide. The resultant heat curable, solvent-soluble prepolymer is used to prepare excellent laminates, moldings, and hard, clear, flexible coatings.

The present invention relates to methods of hydrolyzing alkyl or aryl trialkoxysilanes at neutral conditions to provide organic solvent-soluble, further curable organopolysiloxane prepolymers and thermoset organopolysiloxane prepolymers prepared therefrom.

In the past, it has been difficult to hydrolyze and condense reproducibly organic trifunctional silanes such as methyltrialkoxysilanes by an acid-catalyzed hydrolysis. The amount of acid catalyst such as hydrochloric acid used must be carefully controlled and a slight deviation from an exact prescribed amount as a result of an in advertent mistake can cause a large variation in the polymer produced thereby. The reactions of hydrolysis and condensation are quite fast and sensitive and they generally cannot be easily controlled.

Accordingly, it is an object of the present invention to provide reproducible and economical methods of controllably hydrolyzing organic trifunctional silane monomers such as methyltrialkoxysilane and phenyltrialkoxysilane employing neutral conditions and a hydrolysis catalyst such as diphenoxytitanium oxide or other diaryloxytitanium oxides.

It is an object of the present invention to provide a method of controlling the hydrolysis of an alkyl or aryltrialkoxysilane by employing substantially neutral conditions and a diaryloxytitanium oxide hydrolysis catalyst.

It is an object of the present invention to provide a method of hydrolyzing an organic trialkoxysilane monomer such as methyltrialkoxysilane and preparing a solventsoluble further curable organopolysiloxane prepolymer therefrom, the method including:

(A) Heating a mixture of (1) an organic trialkoxysilane,

(2) an effective amount of a diaryloxytitanium oxide hydrolysis catalyst; and

(3) at least about 1.5 moles of water for every mole of silane at a temperature of about 25 to 160 C. for about 1 to 20 hours to form an organopolysiloxane prepolymer, and

(B) Separating the prepolymer product of Step A from the reaction mixture to obtain a solvent-soluble further curable organopolysiloxane.

It is an object of the present invention to provide a method of hydrolyzing an organic trialkoxysilane monomer and ultimately preparing a thermoset organopolysiloxane from the hydrolyzed prepolymer product, the method including:

(A) Heating a mixture of 3,431,229 Patented Mar. 4, 1969 (l) a silane such as methyltrialkoxysilane, phenyltrialkoxysilane and mixtures thereof,

(2) a diaryloxytitanium oxide hydrolysis catalyst such as diphenoxytitanium oxide in an amount equivalent to about 10 to 200 parts by weight titanium per million parts of silane and water, and

(3) at least about 1.5 moles of water per mole of silane, at a temperature of preferably about to C. for at least about one hour to form an organopolysiloxane prepolymer product having a viscosity equivalent to that of preferably about 30 to 65 centipoises at 60% solids at 25 C. in ethanol, and

(B) Curing the product of Step A at about to 300 C. or higher for at least about one minute to provide a hard, clear, acetone-resistant thermoset organopolysiloxane.

These and other objects will become apparent from the specification that follows and the appended claims.

The present invention provides a method of hydrolyzing an organic trialkoxysilane monomer and preparing a solvent-soluble further curable organopolysiloxane prepolymer therefrom, the method comprising the steps of:

(A) Heating a mixture of (l) a silane which is selected from the group consisting of methyltrialkoxysilane, phenyltrialkoxysilane and mixtures thereof in which the alkoxy group contains 1 to 6 carbon atoms,

(2) an effective catalytic amount of hydrolysis catalyst such as diphenoxytitanium oxide or bis(dodecylphenoxy) titanium oxide; and a (3) at least about 1.5 moles of water for every mole of silane at a temperature of about 25 to C. for about 1 to 20 hours to form an organopolysiloxane partial condensation product prepolymer having a viscosity equivalent to that of about 30 to 300 centipoises at 60% solids at 25 C. in ethanol, and

(B) Separating the resultant prepolymer from Step A to obtain a solvent-soluble further curable organopolysiloxane.

The present invention also provides a method of hydrolyzing an organic trialkoxysilane monomer as above described and preparing a thermoset organopolysiloxanc from the solvent-soluble, further curable prepolymer by curing the prepolymer at about 90 to 300 C. or higher for at least one minute up to 168 hoursor more to pro vide a hard, clear, chemical resistant, thermoset organopolysiloxane.

Suitable diaryloxytitanium oxide catalysts are those in which the aryl radical is obtained from the removal of one hydrogen atom from an aromatic hydrocarbon that preferably has one benzene ring such as phenyl and tolyl. The aryl radical can also be naphthyl or a substituted phenyl group such as dodecylphenyl or other alkylphenyls where the alkyl group contains from 1 to 20 carbon atoms, alkoxy phenyl in which the alkoxy group contains 1 to 8 carbon atoms, and halophenyl where the halogen atom is chlorine, bromine or fluorine including p-chlorophenyl, p-fiuorophenyl and p-bromophenyl. Also suitable, are diaryloxytitanium oxides, mixed titanium oxides in which the aryl radicals are different, e.g., o-methylphenoxy-pdodecylphenoxytitanium oxide.

Of the above diaryloxytitanium oxide, diphenoxytitanium oxide is highly preferred. Also preferred is bisdodecylphenoxytitanium oxide.

The above diaryloxytitanium oxides can be prepared, for instance, by reacting one equivalent weight of a tetraalkoxytitanium such as tetraisopropoxytitanium with two equivalent weights of an aromatic hydrocarbon having a reactive hydroxyl group such as phenol.

Methods of making the diaryloxytitanium oxides are described in my copending application Ser. No. 495,344 filed Oct. 12, 1965, which is incorporated herein by reference.

Generally, at least a trace amount of the catalyst is necessary to obtain the controllable hydrolysis and, hence an amount in the neighborhood of as low as about 0.01 part per million to about 1 or 2 parts by weight of titanium per million parts of silane and water can be used to obtain benefits of the present invention. Usually, about 10 to 200 or 25 parts per million of the titanium content of the catalyst are used although the preferred range is about 20 to 100 parts per million. When the amount of catalyst becomes greater than about 250 parts per million based on the titanium content of the catalyst, the catalyst is being used in excess of that needed which is generally costly and wasteful. Also when too much is used, the catalyst may cause precipitation and/or enough of the titanium atoms will enter the polymer structure to affect adversely the properties of the polymer obtained. While not wishing to be bound by any theory, it is apparently the use of the titanium Lewis acid catalyst, which does not cause precipitation in the reaction mixture, that provides the easy and controllable hydrolysis reaction.

The preferred trifunctional materials are methyltrialkoxysilane or a mixture thereof with phenyltrialkoxysilane in which the alkoxy group is preferably ethoxy. It is preferred that the molar ratio of methyltrialkoxysilanes to phenyltrialkoxysilanes in a mixture of the two is about 2:1 for general molding and coating applications, although generally good results can be obtained using a ratio of about 1.5:1 to 2.5:1. A polymer for laminates in particular, and also coatings and even flexible coatings can also be made with molar ratios of preferably about 1:1 to 1:6 and more preferably about 1:4.

For flexible coating applications, the liquid prepolymers can be dissolved in a solvent, cast and cured in place to provide outstanding coatings. However, for other applications, particularly laminating, it is preferred that the prepolymers be further condensed by heating prior to use.

In general, prepolymers to be further condensed and thereafter spray dried or dried in a wiped film evaporator or otherwise converted to solvent-soluble liquids or solids that are free from gel and, in the case of solids, that are tack free at room temperature are prepared by:

(I) Heating at a pH of 7 a mixture of (A) a silane that is methyltrialkoxysilane, phenyltrialkoxysilane, or mixtures thereof in which the alkoxy radical contains from 1 to 6 carbon atoms and preferably 2 to 3 carbon atoms; and

(B) at least a trace of a hydrolysis catalyst comprising a diaryloxytitanium oxide such as diphenoxytitanium oxide and at least about 1.5 moles of water for every mole of total silane present, at a temperature preferably of about 65 to 85 C. for a period of time of from about 1 to about 10 hours; and

(II) Concentrating the liquid siloxane partial condensation product from Step I to remove some but not all volatile material including alkanol by-product and some water and to obtain a liquid residue having a viscosity equivalent to that of about 30 to 310 centipoises at 60% solids at 25 C. in ethanol.

Thereafter the prepolymer product of Step II is precured or further condensed at a temperature of from about slightly below, say 5 C., to as much as about 50 C. below the gel point of the resin for a period of time of from about seconds to about 60 minutes, the 60 minutes requiring the lower temperature. As previously indicated, the precuring can be accomplished in an economical and quite reproducible manner in a wiped film evaporator by forming a liquid film of the prepolymer product of Step II and heating the same at about 90 to 180 C.

As used here, the gel point is that temperature at which a 50 gram sample of prepolymer gels when placed in a 100 b ak r and stir ed on 600 F. hot P The mixture of methyl and phenyl precured polymers is preferably made by (I) Heating a mixture of (A) from about 1 to about 2 moles of methyltriethoxysilane and from about 6 to about 1 mole of phenyltriethoxysilane;

(B) from about 1.5 to about 3, 4, or even 5 moles of water for every mole of total silane present, there being at least a trace and preferably about 20 parts by weight of titanium in the form of a diaryloxytitanium oxide present in the reaction mixture per million parts of Water and silane at a temperature of about C. for a period of time of from about 2 to about 6 hours; and thereafter, the mixture is further processed by (II) Concentrating the liquid siloxane partial condensation product from Step I by distilling at the reaction temperature until approximately 60-70% of the theoretical yield of ethanol is removed, thereby to remove some but not all volatile material including alkanol by-product and some water and to obtain a liquid residue that in the case of a methylsilane/phenylsilane ratio of about 2.5 :1 to 15:1 has a viscosity of about 30 to 60 or 65 centipoises at 60% solids and 25 C. in ethanol or in the case of a methyl/phenyl ratio of about 1:3.5 to 1:4.5 has a viscosity of about to 310 centipoises; and

(III) Precuring the prepolymer product of Step II preferably by forming a thin film thereof by heating the film to a temperature of about 140 to 190 C. which is a temperature of from about slightly below the gel point to about 30 C. below the gel point of the resin and holding this temperature for a period of time of from about 5 to 10 up to about 120 seconds.

Step III above is preferably accomplished by a heating of the liquid film of a prepolymer having a predetermined gel point of about to 210 C. at about 170 to about or The precured polymer from the methyltrialkoxysilane is generally prepared by a method that includes the steps of (I) Heating at a pH of 7 a mixture of (A) a methyltrialkoxysilane wherein the alkoxy radical contains less than 4 carbon atoms and from 0 to 5 mole percent, based on total silane reactant material, of at least one compound represented by the general formula wherein R in the alkoxy radical OR represents an alkyl radical having less than 4 carbon atoms such as methoxy and ethoxy, and each T independently represents an aryl, alkyl or alkenyl radical, each of which contains less than 7 carbon atoms, or the aforementioned alkoxy radical, OR, and

(B) from 1.5 to about 10 moles and preferably from 2 to about 4 moles of water per mole of total silane and water reactant material, said mixture containing by weight from 10 to 200 parts of titanium in the form of a diaryloxytitanium oxide hydrolysis catalyst per mil lion parts of total silane and water, the heating of the said mixture to form a liquid siloxane partial condensation product being continued for about 1 to about 10 hours at temperatures of at least 50 C. While retain ing in said mixture at least 1.5 moles of alkanol byproduct per mole of silane starting material assuming complete hydrolysis of all alkoxy-silicon linkages in the liquid reaction mixture;

(II) Concentrating the liquid siloxane partial condensation product from Step I by gradually raising its temperature above its initial reaction temperature to a maximum temperature within the range of from about 65 to 300 C. and preferably about 80 to 85 thereby to remove some but not all volatile material including alkanol by-product and some Water and to obtain a liquid residue having a viscosity equivalent to that of about to 35 centipoises at 50% solids at 25 C. in ethanol (which is about 21 to 41 centipoises at 60% solids at 25 C. in ethanol); and

(III) Precuring the concentrated liquid siloxane partial condensation prepolymer product from Step II by heating the product preferably in the form of a liquid film at a temperature of about 140 to 180 C. which is generally slightly below its gelation point to remove the remainder of the volatile material and to obtain, without gelation, a more highly condensed, organic solvent-soluble, siloxane partial condensation precured polymer product that is capable of being finally cured to a solid organopolysiloxane resin. The precured resin, as previously indicated, when solid is also tack free at room temperature and is substantially free from gel. When the precured polymer is liquid, the prepolymer is generally heated from about 85 to 90 C. to about 180 C. preferably in the form of a thin film. The liquid precured product when solidified is also free from gel and capable of forming consistently good flexible coatings.

In preparing a general purpose precured polymer from a mixture of methyl and phenyltrialkoxysilanes in which the ratio of methyl/phenyl is about 1.521 to 25:1, the liquid film is preferably one as described in Step II above that has been further heated to give a viscosity equivalent to that of about 50 to 65 centipoises and optimally, 55 to 60 centipoises, at 60% solids at 25 C. in ethanol, and the heating of the film is preferably conducted at about 160 to 180 C., and optimally, about 165 to 175 C.

Unless otherwise noted, the viscosity in centipoises used herein is that measured with a RVF Brookfield viscometer in accordance with ASTM 219663T, Rheological Properties of Non-Newtonian Liquids.

The following examples are intended to illustrate the present invention and not to limit the same in any way.

EXAMPLE 1 Ingredients Grams Moles Methyltriethoxysilane 71. 2 0. 4 Phenyltriethoxysilane 48. 0 0. 2 Water 24. 3 1. 35 Diphenoxytitanium oxide 0.08

1 About 100 parts titanium per million parts of silane plus water.

The diphenoxytitanium oxide in 8 ml. n-butanol was added to a mixture of the silanes and about /2 the required water (12.0 g.). The solution was taken to reflux when the solution cleared in 30 minutes. The solution was cooled and 12.3 g. of water was added to make a total of 2% moles of water per mole of starting silane. The reaction mixture was then refluxed for a total of four hours to obtain a clear, yellow solution and an organopolysiloxane partial condensation product prepolymer. After the reflux period, Water plus ethanol was distilled from the reaction mixture until the temperature reached 90 C.

A precured further curable polymer having a viscosity of about 60 centipoises at 60% solids at 25 C. in ethanol was obtained. The precured further curable polymer was mixed with enough n-butanol to provide a 50% by weight solids solution, the solution being a clear, pale yellow.

Aluminum panels were dip coated from this solution.

The coatings were heat cured at 220 C. for 7 minutes at a film thickness of 0.5 mil. Excellent hard, clear coatings were obtained. The coatings survived 20% impact elongation tests.

An organopolysiloxane prepared from the same monomers but with an acid catalyst (10 p.p.m. HCI by weight) was tested for comparison. The impact elongation tests were about the same, indicating good impact resistance and flexibility for both the diaryloxytitanium oxide catalyzed and the acid catalyzed polymers.

The above reported impact elongation tests to determine the impact flexibility of the coatings were made with a GE. impact flexibility tester. This instrument generally determines the relative flexibility of a paint, varnish or enamel film expressed as percentage elongation, in a range of 0.5 to 60% as based on the impact of a solid metal cylinder dropped through a guide track from a height of 4 feet onto the reverse side of a coated test panel. The end of the cylindrical impactor is studded with a group of spherical knobs varying in size and calibrated in terms of percent flexibility, based on the elongation or draw they can produce in a metal panel. A reading is made by observing the last indentation in ascending order to show no cracking of the coating.

EXAMPLE 2 A precured polymer was prepared as described in Example 1, only in this case the polymer was prepared from methyltriethoxysilane only, i.e., no phenyltriethoxysilane. Coated aluminum and copper panels were prepared, the results of impact tests being as follows:

Percent Al coated panel 10-20 Cu coated panel 10-20 The film thickness was 0.5 mil; the copper coating was cured at C. for 30 minutes and the aluminum coating was cured at C. for 17 minutes.

Results obtained from coated panels in which the coatings were made from an acid catalyzed solution (described in Example 1) used for comparison were similar.

EMMPLE 4 A precured polymer was prepared as described in Example 1, only in this case the polymer was prepared from phenyltriethoxysilane only, i.e., no methyltriethoxysilane.

Ingredients Grams Moles Phenyltriethoxysilane 35. 5 0. 148 Water 6 66 0. 369 Diphenoxytitanium oxide O. 01

1 50 parts by weight of titanium per million parts of silane and water The diphenoxytitanium oxide, dissolved in 1 ml. of n-butanol, was added to a mixture of the silane and about /2 the required water (3.0 g.). The solution was taken to reflux and cleared within 30 minutes. The solution was cooled and the second portion of the water added (3.66 g. to bring the total moles of water to 0369). Thereafter, the solution was refluxed for four hours, the pot temperature dropping to 82 C.

The reaction mixture was concentrated by heating to 90 C. to remove about 85% of the ethanol and water. The resultant concentrated organopolysiloxane prepolymer solution was diluted with n-butanol to provide a 50% solids solution.

Aluminum panels were coated by the solution to a film thickness of 0.5 mil. The coatings were cured at 300 C.

7 for 30 minutes. Impact elongation tests were as follows:

Percent impact Coating: elongation Acid catalyzed (see Example 1) 2 Diphenoxytitanium oxide catalyzed 2 EXAMPLE 5 An organopolysiloxane was made from the following formulation:

50 parts by weight titanium per million parts of silane and water Diphenoxytitanium oxide Was added to the mixture of silanes and water, and the solution refluxed for 60 minutes resulting in a clear solution. Solution refluxed four hours longer after pot temperature had dropped to 80 C. The solution was cooled to room temperature and filtered and the clear yellow solution was concentrated until pot temperature reached 90 C. to remove about 85% of the ethanol and water. To the resultant concentrated organopolysiloxane prepolymer solution was added xylene (50 ml.) and the solution further heated in an open beaker to about 180 C. This viscous further condensed polymer was dissolved in xylene to provide a 50% solids solution.

Style 181 heat clean and neutral pH E-glass cloth was dipped in the 50% solution and air dried for 2 hours. The cloth was then cut into squares 7 x 7"; these were stacked to give 14 plies and the stacks placed in a press preheated to 400 F. Slight pressure was applied until resin gelled (45 minutes) and the pressure increased to 500 p.s.i. After 30 minutes the press was cooled to 200 F. and the laminate removed. The resin pick up was 22% by weight.

The laminates were run through a heating cycle and tested, the heating cycle being as follows:

Hours: C.

The laminates were tested at room temperature, the fiexural strength being 41,800 p.s.i. and the tangent modulus 3.37 l0 p.s.i. Laminates were again tested at room temperature after further heating at 300 C. for 200 hours and Were found to have a flexural strength in the neighborhood of about 30,000 p.s.i. and tagent modulus of about 3.1 x p.s.i.

The hydrolysis and condensation reactions of Example 1 Were attempted by using water alone (no catalyst). The reaction mixture did not form clear solutions over a period of 6 hours at 85 C. and hence the reactions were undesirable without the diaryloxytitanium oxide hydrolysis catalyst.

In the above examples, other diaryloxytitanium oxides previously described such as ditolyloxytitanium oxide, di(p-chlorophenoxy)titanium oxide, dinaphthyloxytitanium oxide and bis(dodecylphenoxy)titanium oxide, can be used as the hydrolysis catalyst to provide substantially similar results.

It is to be understood that various modifications of l organopolysiloxane prepolymer therefrom, the method comprising the steps of:

(A) heating a mixture of (1) a silane which is selected from the group consisting of methyltrialkoxysilane, phenyltrialkoxysilane and mixtures thereof in which the alkoxy group contains 1 to 6 carbon atoms;

(2) an effective catalytic amount of a diaryloxytitanium oxide hydrolysis catalyst; and

(3) at least about 1.5 moles of water for every mole of silane at a temperature of about 25 to 160 C. for about 1 to 20 hours to form an organopolysiloxane partial condensation product prepolymer having a viscosity equivalent to that of about 30 to 310 centipoises at 60% solids at 25 C. in ethanol; and

(B) separating from the reaction mixture the resultant prepolymer from Step A to obtain a solvent-soluble further curable organopolysiloxane.

2. A method of hydrolyzing an organic trialkoxysilane monomer and preparing a thermoset organopolysiloxane therefrom, the method comprising the steps of:

(A) heating a mixture of (1) a silane which is selected from the group consisting of methyltrialkoxysilane, phenyltrialkoxysilane and mixtures thereof in which the alkoxy group contains 1 to 6 carbon atoms,

(2) an effective catalytic amount of a diaryloxytitanium oxide hydrolysis catalyst, and

(3) at least about 1.5 moles of water for every mole of silane at a temperature of about 25 to 160 C. for about 1 to 20 hours to form an organopolysiloxane partial condensation product prepolymer having a viscosity equivalent to that of about 30 to 310 centipoises at 60% solids at 25 C. in ethanol, and

(B) curing the product of Step A at about to 300 C. for at least about one minute to provide a thermoset organopolysiloxane.

3. A method as defined in claim 1 in which the organopolysiloxane of Step B is mixed with an Organic solvent therefor to obtain a solids content of about 20 to 60% by weight.

4. A method as defined in claim 3 in which the solution of claim 3 is applied to a surface to form a solid layer which is cured at about to 300 C. to form a hard acetone resistant coating.

5. A method as defined in claim 1 in which the product of Step B is further condensed at about 90 to 200 C. to provide an organic solvent-soluble, further curable organopolysiloxane.

6. A method as defined in claim 5 in which the further curable organopolysiloxane is a solid.

7. A method as defined in claim 5 in which the further curable organopolysiloxane is a viscous liquid.

8. A method as defined in claim 1 in which the silane is methyltriethoxysilane.

9. A method as defined in claim 1 in which the silane is a mixture of methyltriethoxysilane and phenyltriethoxysilane.

10. A method as defined in claim 1 in which the silane is phenyltriethoxysilane.

11. A method as defined in claim 1 in which the hydrolysis catalyst is used in an amount of about 10 to 200 parts by weight of titanium per million parts by weight of silane and water.

12. A method as defined in claim 1 in which the hydrolysis catalyst is used in an amount of about 20 to 100 parts by weight of titanium per million parts of silane and water.

13. A method as defined in claim 1 in which the hydrolysis catalyst is a diaryloxytitanium oxide in which the aryl group is the residue of an aromatic hydrocarbon after the removal of a hydrogen atom.

14. A method as defined in claim 13 in which the residue of the aromatic hydrocarbon is phenyl.

15. A method as defined in claim 13 in which the residue of the aromatic hydrocarbon is tolyl.

16. A method as defined in claim 13 in which the residue of the aromatic hydrocarbon is naphthyl.

17. A method as defined in claim 1 in which the hydrolysis catalyst is a diaryloxytitanium oxide in which the aryl group is a substituted aromatic hydrocarbon.

18. A method as defined in claim 17 in which the residue of the substituted aromatic hydrocarbon is an alkylphenyl wherein the alkyl group has 1 to 20 carbon atoms.

19. A method as defined in claim 18 in which the alkylphenyl is dodecylphenyl.

20. A method as defined in claim 17 in which the residue of the substituted aromatic hydrocarbon is a member selected from the group of alkylphenyl in which the alkyl group has 1 to 20 carbon atoms, alkoxyphenyl in which the alkyl group has 1 to 8 carbon atoms, and halogensubstituted phenyl.

21. A method as defined in claim 2 in which the hydrolysis catalyst is diphenoxytitanium oxide.

22. A method as defined in claim 2 in which the hy drolysis catalyst is bisdodecylphenoxytitanium oxide.

23. A method as defined in claim 1 in which the heating of Step A is at about 90 C. for about 4 hours.

24. A method as defined in claim 2 in which the prepolymer of Step B is cured at about 90 C.

25. A method as defined in claim 3 in which the organic solvent is n-butanol.

26. A method as defined in claim 3 in which the organic solvent is xylene.

References Cited UNITED STATES PATENTS 2/1968 Newing 260--46.5 6/1968 Burzynski et al 26032.8

US. Cl. X.R. 

